412047-63-3Relevant academic research and scientific papers
Chemistry of highly electrophilic binuclear cations. 2. Oxidation reactions of [W2(η5-C5 H5)2(CO)4(μ-Ph2PCH2 PPh2)] with [FeCp2][B{3,5-C6H3 (CF3)2}4]
Alvarez, M. Angeles,Anaya, Yvonne,Garcia, M. Esther,Riera, Victor,Ruiz, Miguel A.,Vaissermann, Jacqueline
, p. 456 - 463 (2008/10/08)
Chemical oxidation of the title compound [W2Cp2(CO)4(μ-dppm)] (Cp = η5-C5H5; dppm = Ph2PCH2PPh2) with 1 equiv of [FeCp2](BAr′4) (Ar′ = 3,5-C6H3(CF3)2) leads to the tetracarbonyl radical [W2Cp2(CO)4(μ-dppm)] (BAr′4), which experiences spontaneous decarbonylation to give the 31-electron radical [W2Cp2(μ-CO)(CO)2 (μ-dppm)](BAr′4). Oxidation of [W2Cp2(CO)4(μ-dppm)] with 2 equiv of [FeCp2](BAr′4) gives the tricarbonyl derivative [W2Cp2(μ-CO)(CO)2-(μ-dppm)] (BAr′4)2. The same result is obtained when oxidizing the radical [W2Cp2(μ-CO)(CO)2(μ-dppm)] (BAr′4) with [FeCp2](BAr′4). The triply bonded complex [W2Cp2(μ-CO)(CO)2 (μ-dppm)](BAr′4)2, which displays fluxional behavior in solution, reacts with P(OMe)3 to give [W2Cp2(μ-CO)(CO){P(OMe)3}(μ-dppm)] (BAr′4)2, the structure of which has been solved through a single-crystal X-ray diffraction study. Reaction of [W2Cp2(μ-CO)(CO)2(μ-dppm)] (BAr′4)2 with salts of halide ions X- (X = Cl, Br, I) gives the corresponding halo derivatives [W2Cp2(μ-X)(μ-CO)(CO)2(μ-dppm)] (BAr′4). When X = I, a mixture of two isomers differing in the relative positions of the bridging halide and carbonyl is obtained. The same halide compounds were obtained in the reactions of paramagnetic [W2Cp2(μ-CO)(CO)2(μ-dppm)] (BAr′4) with halogens X2. The tricarbonyl radical was found to react slowly with water to give the known hydroxycarbyne derivative [W2Cp2(μ-COH)(CO)2(μ-dppm)] (BAr′4).
Reactivity of the carbyne complexes [W2(μ-COR)(η5-C5H5)2 (CO)2(μ-Ph2PCH2PPh2)]+ (R = H, Me) toward diazomethane
Alvarez, M. Angeles,García, M. Esther,Riera, Víctor,Ruiz, Miguel A.,Robert, Francis
, p. 1177 - 1183 (2008/10/08)
Reaction of [W2(μ-COH)Cp2(CO)2(μ-dppm)]BF2 (Cp = η5-C5H5; dppm = Ph2PCH2PPh2) with CH2N2 in the presence of CuCl at -75 °C leads to the methoxycarbyne cluster [CuW2Cl(μ3-COMe)Cp2(CO)2(μ-dpp m)]BF4. Copper(I) chloride can be cleanly removed from the latter upon addition of PPh3, thus giving the methoxycarbyne complex [W2(μ-COMe)Cp2(CO)2(μ-dppm)]-BF4 . In the absence of CuCl, either the hydroxy or the methoxycarbyne ditungsten cations react with CH2N2 to give a mixture of the μ-methylene, μ-alkenyl compound [W2(μ-CH2){μ-η1:η2-C(O Me)=CH2}Cp2(CO)2(μ-dppm)]BF4, which has been characterized through an X-ray study, and the μ-alkyne, μ-alkenyl species [W2{μ-η1:η2-C(OMe)CH}{μ-η 1:η2-C(OMe)CH2}Cp2-(CO)(μ-dpp m)]BF4, the latter being the result of the addition of four molecules of CH2N2 to the starting hydroxycarbyne compound. The influence of experimental conditions on the above reactions has been analyzed through separate experiments. For example, the use of tetrahydrofuran as solvent almost suppresses the formation of the alkyne product, whereas the use of a noncoordinating anion such us [B{3,5-C6H3(CF3)2}4] - instead of BF4- as counterion precludes the reaction to occur beyond the methoxycarbyne compound. The solution structures of the new compounds are analyzed in the light of the IR and NMR spectra, and plausible reaction pathways are proposed in order to explain the formation of the reaction products.
